Vegetable oil derivatives as lubricant additives

ABSTRACT

There is disclosed a lubricating composition consisting essentially of a lubricant base and a lubricant additive wherein the lubricant additive comprises at least two groups of ingredients, wherein, the first group is a triglyceride vegetable oil, a wax ester of a triglyceride vegetable oil and combinations, the second group is a sulfurized mixture of a triglyceride vegetable oil and a wax ester of a triglyceride vegetable oil, and the third group is a phosphite adduct of triglyceride vegetable oil, a phosphite adduct of wax ester and combinations.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.07/606,522, filed Oct. 31, 1990, now abandoned, which is a divisionalapplication of U.S. patent application Ser. No. 07/282,014, filed Dec.9, 1988, now U.S. Pat. No. 4,970,010, which is a continuation-in-part ofU.S. patent application Ser. No. 221,061, filed Jul. 19, 1988, now U.S.Pat. No. 4,925,581.

TECHNICAL FIELD

The present invention relates to lubricant compositions and lubricantadditives and to methods for producing lubricant additives withantifriction properties that contain vegetable oil and vegetable oilderivatives as lubricating agents. More specifically, this inventionrelates to wax esters of vegetable oil fatty acids, sulfurized vegetableoil triglycerides, sulfurized vegetable oil wax esters, vegetable oiltriglycerides, phosphite adducts of vegetable oil triglycerides, andphosphite adducts of vegetable oil wax esters as lubricant additives invarious combinations, and from various vegetable oil sources.

BACKGROUND OF THE INVENTION

Lubricants are widely used to reduce the friction between the surfacesof moving parts and thereby reduce the wear and prevent damage to theparts. Most lubricants are comprised principally of a base stock whichis generally a relatively high molecular weight hydrocarbon. Inapplications where the amount of pressure applied to the moving part isquite high, lubricants which are comprised of only hydrocarbon basestock tend to fail and the contacting parts are damaged. It is wellknown to add materials (lubricant additives) to increase the highpressure performance of lubricants. These materials are generally called"extreme pressure additives." Examples of extreme pressure additives aresulfurized materials such as sulfurized sperm whale oil or sulfurizedjojoba oil.

Wax esters can be sulfurized from natural wax esters, such as fromjojoba oil, and from synthesized wax esters, such as from vegetable oiltriglycerides and liberated fatty acids. Natural wax esters haveproduced formulated sulfurized products that provide effective lubricantadditive compositions. However, the problems with the natural wax estersare availability and cost. The vegetable oils have to be transesterifiedfrom the free fatty acids to produce the wax esters. For practicalapplications, however, the vegetable oil triglycerides have thedisadvantage that cost-adding conversion steps are necessary to form awax ester for sulfurization, rather than a direct sulfurization of thetriglyceride. These extra processing steps make vegetable oil wax estersrelatively uneconomical as lubricant additives.

Princen et al., "Development of New Crops for Industrial Raw Materials,"J. Amer. Oil Chemists Soc., 61: 281-89, 1984, tried to sulfurizemeadowfoam oil by sulfurizing the wax esters of the meadowfoam fattyacids. Princen et al. found that sulfurization of the unalteredtriglyceride oil can react with sulfur under traditional sulfurizationconditions to yield factice, a solid chemical rubber and an unacceptablelubricant additive. Factice forms due to cross-linking of hydrocarbonchains by polysulfide bonds to create an insoluble material. The firstsulfurized wax ester of meadowfoam oil preparation in Princen et al. hadgood lubrication properties, but it corroded copper, foamed excessively,and thickened excessively under in-use conditions in a hot gear box. Thesecond sulfurized wax ester of meadowfoam oil preparation in Princen etal. was made with different synthesis conditions, but the secondpreparation decreased copper corrosion and maintained lubricatingproperties but produced more foam and did not meet a thermal stabilitytest. The third preparation in Princen et al. used wax esters fromenriched monoene and diene acids. The diene wax ester (made frommonoenoic fatty acids) resulted in increased wear scar but favorableother properties.

Wakim, U.S. Pat. No. 3,986,966, after demonstrating that sulfurizationof triglycerides alone gave resinous products mostly insoluble in baseoils, added nonwax methyl esters of a fatty acid of 18 to 22 carbonatoms which are monounsaturated to improve the solubility of thesulfurized triglycerides.

Hutchinson et al., U.S. Pat. No. 3,740,333 refers to sulfurized blendsof lard oil and a saturated wax ester, the essential element of the waxester being derived from a C₁₀₋₁₆ saturated alcohol and a C₁₈₋₂₂unsaturated acid.

Kammann et al., "Sulfurized Vegetable Oil Products as LubricantAdditives," J. Amer. Oil Chemists Soc., 62:917-23, 1985, found thatsulfurized vegetable triglyceride oils resulted in rubbery products, insome cases even at a 12% sulfur content. Kammann et al. tried usingsulfurization with large amounts of methyl lardate, but obtained facticeor near factice with meadowfoam oil. Kammann et al. was able tosulfurize only by adding 10% unsaturated oleic acid beforesulfurization; however, the resulting product properties wereundesirable as a lubricant additive.

There are many problems using a sulfurized vegetable oil and extraexpenses making a wax ester from a triglyceride vegetable oil.Therefore, there exists a need in the art to find lubricant additivecompositions that can use the relatively abundant supplies of vegetableoils without resorting to the multiple processing steps of making waxesters of the fatty acids. There further exists a need in the art to beable to sulfurize triglyceride vegetable oils for use as lubricantadditives.

SUMMARY OF THE INVENTION

Briefly stated, the present invention encompasses lubricant additivescomprising combinations of triglyceride vegetable oil with at least oneof a sulfurized vegetable oil and a phosphite adduct of vegetable oil.The vegetable oil is a triglyceride in its native state with the fattyacids having from about 16 to about 26 carbon atoms and at least onedouble bond, but no more than three double bonds for at least 90% of thefatty acids. Preferably, the vegetable oil fatty acids are C₁₈₋₂₂ withthe majority of fatty acids having one double bond. Most preferably, thevegetable oil is meadowfoam oil, rapeseed oil or crambe oil.

The vegetable oil can be in the form of the native triglyceride or as amixture with vegetable oil wax ester. The sulfurized vegetable oilcomprises either a sulfurized mixture of the triglyceride form of thevegetable oil with from about 25% to about 75% of a wax ester orsulfurized vegetable oil wax ester. The wax ester for mixing with thetriglyceride vegetable oil for sulfurization is jojoba oil or is derivedfrom a C₁₈₋₂₂ unsaturated fatty acid and a C₁₈₋₂₂ unsaturated fattyalcohol. Preferably, the wax ester is a naturally occurring wax ester,such as jojoba oil, or the wax ester of meadowfoam oil or rapeseed oil.The phosphite adduct of the vegetable oil can be a mono- throughhexa-adduct of the triglyceride form of the vegetable oil, or a mono-through tetra-adduct of the wax ester form of the vegetable oil.

The phosphite adduct of the vegetable oil is formed by the reaction ofthe native triglyceride vegetable oil or wax ester of the vegetable oiland a compound of the formula: ##STR1## wherein R is H, C₁₋₁₂ alkyl,C₁₋₁₂ aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₄₋₁₂ alkyl.Preferably, R is C₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, or cyclo C₄₋₈alkyl. Most preferably, R is n-butyl.

The present invention further comprises a lubricating compositionconsisting essentially of a lubricant base and a lubricant additivewherein the lubricant additive comprises a mixture of at least twoingredients from different classes of ingredients selected from thegroup consisting of three classes of ingredients:

wherein the first class of ingredients comprises a triglyceridevegetable oil, a wax ester of the vegetable oil, and a combinationthereof;

wherein the second class of ingredients comprises: a sulfurizedvegetable oil wax ester; a sulfurized triglyceride vegetable oil withinthe range of from about 25% to about 75% vegetable oil, and from about25% to about 75% of a wax ester, as described herein; and a combinationthereof; and

wherein the third class of ingredients comprises a phosphite adduct oftriglyceride vegetable oil, a phosphite adduct of the vegetable oil waxester, and a combination thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is a lubricant with anti-friction properties,including antiwear and load-carrying properties, and comprising alubricant base and a lubricating additive. The lubricant base stock canbe selected from a large class of compounds. Most often the base is ahigh molecular weight hydrocarbon. The lubricant base is, preferably, amineral oil, although synthetic hydrocarbon lubricating oils and othersynthetic lubricating oils, such as ester lubricating oils and mixturesthereof (e.g., mixtures of mineral and synthetic lubricating oils), canalso be used, provided that the desired proportion of lubricatingadditive is soluble in the lubricant base. The mineral oils include HVI(high viscosity index) oils, Bright Stock, and Bright Stock extract aswell as MVI and LVI oils. The viscosity index of these oils can varyfrom -150 to 150. The 210° F. viscosities of these oils can vary from 2to 140 centistokes. Mixtures of these oils are also suitably employed.

Examples of lubricant bases include hydrocarbon oil; synthetichydrocarbon; an ester-based lubricant; a mineral oil; a mixture of amineral oil and an ester-based lubricant; a mixture of mineral oil,synthetic hydrocarbon, and an ester-based lubricant; a mineral oil-basedgrease; and a synthetic hydrocarbon-based grease. Specifically, the basefluids are:

a. mineral oils, such as paraffinic neutral 100", furfural-refinedparaffinic oil, solvent-refined napthenic oil, and solvent-refinedaromatic oil;

b. synthetic hydrocarbon oils, such as hydrogenated or partiallyhydrogenated polydecene and other olefins, hydrogenated hexene oligomer,hydrogenated octene oligomer, hydrogenated decene oligomer, hydrogenatedC₆₋₁₀ oligomer, and hydrogenated C₈₋₁₀ oligomer;

c. ester fluids, such as pentaerythritol esters having the structures:##STR2## wherein R is C₄ H₉, C₆ H₁₃, C₈ H₁₇, or mixtures thereof; estersof trimethylolpropane and dipentaerythritol of the structures: ##STR3##wherein R is defined as above; di-2-ethylhexyladipate;di-2-ethylhexylsebacate; didecyladipate; and didecylsebacate;

d. dialkylbenzenes, such as didocecylbenzene;

e. polyglycols, such as UCON fluids, polypropylene glycols of 1000 to3000 molecular weight and polyethylene glycols of 1000 to 3000 molecularweight;

f. alkylaromatics; and

g. dicarboxylic acids.

The lubricating additives of the present invention can be used with avariety of lubricating compositions, such as cutting fluids, precoatoils, metal-working oils, ATFs (automatic transmission fluids), gearoils, way lubricants, greases, aviation oils, textile lubricants,hydraulic oils, circulating oils, steam cylinder oils, spindle oils,fire-resistant fluids, and automotive and marine oils.

Vegetable oils useful for the present invention are a tri-ester of threelong chain unsaturated fatty acids with glycerol, a tri-hydroxy alcohol.Jojoba oil, by contrast, is a monoester of a long chain unsaturated acidand a long chain unsaturated alcohol. The fatty acids are from about 16to about 26 carbon atoms in length and are at least monounsaturated andnot more than triunsaturated for at least 90% of the vegetable fattyacids. Preferably, the vegetable oil fatty acids are C₁₈₋₂₂ with themajority of fatty acids being monounsaturated. Most preferably, thevegetable oil is meadowfoam oil, rapeseed oil or crambe oil. Otheruseful vegetable oils include: soya bean oil, peanut oil, safflower oil,sunflower seed oil, cottonseed oil, olive oil, corn oil, coconut oil,palm oil and the like.

Meadowfoam (Limnanthes laba) is a herbaceous winter annual plant nativeto the Pacific Northwest region of the United States. The common name"meadowfoam" was given because of the appearance of its solid canopy ofcreamy white flowers at full bloom. Meadowfoam is currently being growncommercially in Oregon's Willamette Valley.

Meadowfoam oil is extracted from meadowfoam seeds. Meadowfoam seeds arepear-shaped, consisting of a thin, brown, striated hull surrounding arelatively soft, light-colored dicotyledon kernel. The seeds, measuringabout 2×3 mm, average about 150 to the gram. The kernels contributeabout two-thirds of the total weight and contain essentially all of thetriglyceride oil. Commercial meadowfoam seeds generally contain about27% oil.

Meadowfoam oil is a triglyceride with approximately 95% of the fattyacids being C₂₀ and C₂₂ fatty acids and primarily monoenoic (singleunsaturation). Further, there is a lack of conjugation of even thedienoic fatty acids, as the double bonds are located far from eachother. This amount of unsaturation provides for greater oxidativestability than is found in conjugated, unsaturated fatty acids.Meadowfoam oil triglyceride has the α- and α'-positions usually occupiedby 5' monoenoic acids and the major fatty acids are: 5-eicosenoic,11-eicosenoic, 5-docosenoic, 13-docosenoic, and 5,13-docosadienoicacids.

Meadowfoam oil, for example, contains about 20% diene in the acidportion of the molecule. An example of this diene structure is5,13-docosadienoate ester of glycerol: ##STR4## The diene structure isbelieved to be the major cause for problems in the art sulfurizingmeadowfoam oil to a soluble product, particularly when high levels(i.e., >10% sulfur) are used. The sulfurization problem is due tocross-linking. For example, when triglyceride meadowfoam oil issulfurized for two hours at 180° C., using 20 weight percent of sulfurusing standard procedures, the resulting product is incompletely solublein a hydrocarbon oil. This result is consistent with publishedobservations of sulfurizing triglyceride meadowfoam oil (see Kammann etal. supra).

Rapeseed oil comes from Brassica nopus and typically has a fatty acidcomposition of:

    ______________________________________                                                18:1  13%                                                                     18:2  11%                                                                     18:3   5%                                                                     20:1  10%                                                                     22:1  55%                                                                     Other  6%                                                             ______________________________________                                    

Crambe abyssinica (crambe oil) is native to Mediterranean countries andtypically has a fatty acid composition of:

    ______________________________________                                                18:1  17%                                                                     18:2   9%                                                                     18:3   6%                                                                     20:1   5%                                                                     22:1  55%                                                                     Other  8%                                                             ______________________________________                                    

The sulfurized vegetable oils of the present invention are completelysoluble in hydrocarbon and comprise from about 25% to about 75% of thevegetable oil in the triglyceride form and from about 75% to about 25%of a wax ester, wherein the wax ester is jojoba oil or is derived from aC₁₈₋₂₂ unsaturated acid and a C₁₈₋₂₂ unsaturated alcohol. Preferably,the wax ester is jojoba oil or a wax ester of meadowfoam oil, rapeseedoil or crambe oil. The combination of triglyceride vegetable oil such asmeadowfoam oil and jojoba oil or a wax ester can be sulfurized at highsulfur concentrations, such as 20 weight percent of sulfur. Thesulfurization concentrations are from about 10% to about 25% sulfur.Preferably, the sulfur concentration is from 12% to about 20%. Forexample, Table 1 illustrates the solubility and copper strip testresults of sulfurized combinations of triglyceride meadowfoam oil andjojoba oil (as the wax ester).

                  TABLE 1                                                         ______________________________________                                        Sulfurized Combinations of Meadowfoam                                         Oil and Jojoba Oil                                                                                          Solubility                                                                             Copper                                                      Sulfur   in 5%    Strip                                  Run # Oil (grams)    (grams)  Mineral Oil                                                                            Test                                   ______________________________________                                        1.    20 jojoba oil  4        soluble  2B                                     2.    20 meadowfoam oil                                                                            4        insoluble                                                                              --                                     3.    20 meadowfoam oil                                                                            3        hazy     3C                                     4.    15 jojoba oil +                                                                5 meadowfoam oil                                                                            4        soluble  2A                                     5.    10 jojoba oil +                                                               10 meadowfoam oil                                                                            4        soluble  2A                                     6.     5 jojoba oil +                                                               15 meadowfoam oil                                                                            4        soluble  1B                                     ______________________________________                                    

The copper strip test is graded as follows: 1A, 1B, 2A and 2B are brightcopper; 3A, 3B and 3C are stained copper; 4A and 4B are purple stainedcopper; and 5A and 5B are black copper.

A portion of the acid segment of meadowfoam oil has two double bandspresent. When there are two double bonds in the same acid portion of thetriglyceride molecule, as for example in meadowfoam oil or rapeseed oilor crambe oil, the result on sulfurization of the triglyceride atapproximately 10% sulfur concentration is to produce a solid or veryviscous product with limited solubility in hydrocarbon oils. Such asolid or very viscous product would not be an acceptable lubricantadditive. The solid or very viscous product is formed due tocross-linking with sulfur and each other, such that some molecules maybe produced which have large quantities of sulfur and small amounts ofsolubilizing ester or glyceride. The preferred wax ester for adding totriglyceride meadowfoam oil for sulfurizing, jojoba oil, has two doublebonds in the molecule but one double bond is in the acid portion of themolecule and the second double bond is in the alcohol portion of themolecule, far removed from the first double bond. Thus, jojoba oilbehaves differently from meadowfoam oil, rapeseed oil or crambe oil.

Jojoba oil appears to be reacting with an intermediate to provide asolubilizing effect of the final product in hydrocarbon oils. Acomparison of the sulfurized product of U.S. Pat. No. 3,986,966 with asaturated nonwax ester and the present invention with a wax ester (e.g.,jojoba oil) and a triglyceride (rapeseed oil or meadowfoam oil) is asfollows:

                  TABLE 2                                                         ______________________________________                                        C.sub.14- 15 Alkyl Oleate                                                                Table V of                                                                    U.S. Pat.                                                                     No. 3,986,966                                                                            Jojoba Oil                                              ______________________________________                                        Alcohol portion                                                                            14-15 (saturated)                                                                          20-22 (unsaturated)                                 of ester                                                                      Fatty oil    Rapeseed     Meadowfoam                                          Ester/oil ratio                                                                            1.22:1       1.22:1                                              Sulfur, wt.% 9.5          17.7                                                Viscosity at 2075         1189                                                100° F. SUS                                                            Copper corrosion                                                                           1B           1A                                                  3 hrs. at 212° F.                                                      Solubility   cloudy       clear                                               ______________________________________                                    

Despite the use of a molecule with two double bonds, the inventivecombination for sulfurizing, provide a product with superior solubilitycharacteristics in hydrocarbon oil.

Triglyceride meadowfoam oil can be converted to the wax ester form by aprocess of treating the triglyceride with LiAlH₄ or another reducingagent into meadowfoam alcohols, such as:

    CH.sub.3 (CH.sub.2).sub.n CH═CH(CH.sub.2).sub.3 CH.sub.2 OH

wherein n is 13 or 15 and glycerol is a by-product. The meadowfoamalcohols are added to the triglyceride meadowfoam oil in the presence ofacid and heat to form more glycerol as a by-product and a meadowfoam waxester:

    CH.sub.3 (CH.sub.2).sub.n CH═CH(CH.sub.2).sub.3 COOCH.sub.2 (CH.sub.2).sub.3 CH═CH(CH.sub.2).sub.n CH.sub.3

wherein n is 13 or 15. Meadowfoam wax ester is structurally analogous tojojoba oil (except for the location of the double bonds) and is amixture of long straight chain esters with 40 to 44 carbon atoms. As astructural analog to jojoba oil, meadowfoam wax esters have similarchemical properties to jojoba oil. Other vegetable oil triglycerides maybe converted to the wax ester form by the same or similar processes. Theresulting wax esters of rapeseed oil and crambe oil are chemicallysimilar to the wax ester of meadowfoam oil.

Many sulfurized wax esters of vegetable oils may be used in combinationwith the lubricant additives of the present invention. A preferredsulfurized wax ester of a vegetable oil is the product of a reaction ofthe vegetable oil and 12% to 20% sulfur to yield the following: ##STR5##and mixtures of both, wherein n is an integer from 1 to 3, and A refersto the vegetable wax ester.

For example, twenty grams of meadowfoam wax ester was sulfurized with 4grams of sulfur at 180° C. for 2 hours under nitrogen with stirring. Theresulting sulfurized meadowfoam wax ester was soluble at a 5%concentration in mineral oil and had a 2B score in the copper striptest. Similarly, 20 grams of meadowfoam wax ester sulfurized in the sameconditions with 3 grams of sulfur was soluble at a 5% concentration inmineral oil and had a 2A score in the copper strip test.

The phosphite adduct of the vegetable oil is formed by the reaction oftriglyceride vegetable oil or a wax ester of a vegetable oil and acompound of the formula: ##STR6## wherein R is H, C₁₋₁₂ alkyl, C₁₋₁₂aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₁₋₁₂ alkyl. Preferably, Ris C₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, or cyclo C₄₋₈ alkyl. Mostpreferably, R is n-butyl.

As may be seen from the structural formulae, vegetable oil wax esters ofthe present invention have either two, three, or four carbon-carbondouble bonds. Accordingly, the phosphite adduct of the wax ester of thevegetable oil can be either a di-adduct, a tri-adduct, or a tetra-adductof the wax ester of the vegetable oil.

The triglyceride form of native vegetable oil can have between three andsix carbon-carbon double bonds within the three fatty acids on theglycerol backbone. In extremely rare instances, there could be as manyas nine double bonds. Therefore, depending upon the amount of phosphiteadded as a reactant for the triglyceride vegetable oil, the phosphiteadduct of triglyceride vegetable oil can be a mono-, di-, tri-, tetra-,penta-, or a hexa-adduct. The penta-adduct should be a rare species andthe hexa-adduct an extremely rare species according to Poissondistribution probabilities, because the frequency of dienes among thepreferred vegetable oil fatty acids (i.e., meadowfoam, rapeseed, andcrambe oils) is only approximately 20%. Thus, the tri-adduct should bethe most common species. The preferred products are the mono-, di-, andtri-adducts.

The following are examples of species of the phosphite adduct ofmeadowfoam oil wax ester: ##STR7## wherein n is 13 or 15.

The following are examples of species of the phosphite adduct ofmeadowfoam oil triglyceride: ##STR8## wherein n is 13 or 15.

The present invention further relates to lubricating compositions,containing a lubricant additive. Depending upon the application and thedesired extent of antiwear protection, the total additive concentrationwill range from about 0.1% to about 25% by weight. The lubricantadditive comprises a combination of a vegetable oil as the triglycerideor was ester or a combination of both (but not necessarily from the samevegetable oil source), and at least one of a sulfurized vegetable oil,as described herein, and/or a phosphite adduct of a vegetable oil aseither the wax ester or the triglyceride or a combination of both, asdescribed herein. Preferably, the lubricant additive comprisesmeadowfoam, rapeseed or crambe oil as a triglyceride, meadowfoam oiltriglyceride in combination with jojoba oil and sulfurized at about 20%sulfur, and the phosphite adduct of meadowfoam oil triglyceride. Theinventive lubricant additive can substitute a phosphite adduct of jojobaoil as described in copending U.S. patent application Ser. No. 088,186,filed Aug. 21, 1987 and incorporated by reference herein.

Depending upon the application of the final lubricant product and thedesired extent of antiwear protection desired, the total lubricantadditive concentration will vary from about 0.1% to about 25% by weight.For example, a lubricant additive may contain about 0.1% to about 5.0%of a triglyceride vegetable oil, a wax ester vegetable oil or acombination of both; about 0.2% to about 10.0% of sulfurized vegetableoil as defined herein; and from about 0.1% to about 5.0% of thephosphite adduct of a vegetable oil as defined herein. Preferably, thephosphite adduct of the vegetable oil is a monoadduct ofdibutylphosphite of triglyceride vegetable oil.

Different combinations and concentrations of the lubricant additivecomponents will depend upon the desired product attributes. For example,a hydraulic oil would have a lubricant additive comprising (percentagesare by weight of total product) a relatively low concentration of thesulfurized vegetable oil (as defined herein) of about 0.1% to about0.5%, a relatively high concentration of the triglyceride vegetable oil(approximately 2%) and a relatively low concentration of the phosphiteadduct of the vegetable oil (as defined herein) of approximately 0.5%. Ametal cutting oil, for example, would have a lubricant additivecomprising (percentages are by weight of total product) approximately 7%sulfurized triglyceride oil (as defined herein), and approximately 2% ofthe triglyceride vegetable oil and optionally approximately 0.5% of aphosphite adduct of the vegetable oil (as defined herein). An automotiveengine oil, for example, would contain a lubricant additive comprising(percentages are by weight of total product) approximately 1% sulfurizedvegetable oil (as defined herein) approximately 2% of the triglyceridevegetable oil, approximately 0.5% of the phosphite adduct of thetriglyceride vegetable oil (as defined herein) and other additives asare normally used in an automotive engine oil.

The following example illustrates test model performance results fromstandard test including the 4-Ball Wear Test and the Falex Wear Test.The 4-Ball Wear Test assesses extreme pressure properties of thelubricant. The measurement of friction as related to rolling, drawing,and other metal-working operations depends upon the surface of the tooland workpiece and the viscosity and chemical makeup of the lubricant, aswell as the pressure and temperature developed during processing. The4-Ball wear test machine provides, under controlled testing conditions,a procedure for measuring friction. The machine consists of three ballstouching each other and clamped together in a horizontal plane. A fourthball touches three clamped balls by being positioned between the threeand is driven by a motor so that it revolves in contact with the clampedballs. The rotation takes place within a reservoir containing a testlubricant. A temperature-measuring device, as well as a heater, providesa method for controlling the temperature of the test fluid. The rotatingball is loaded and then rotated for a specific time at a specific speed.At the conclusion of the test, the scar patterns developed on the ballsare measured. Any stains are observed, the diameter of the scar ismeasured, and the coefficient of friction is calculated by dividing thetangential force by the normal force at the ball surface.

The Falex test consists of a method for measuring the torque andfriction developed during rotation of a pin between two stationary Vblocks. The pin as well as the V blocks can be made of variousmaterials. The temperature of the lubricant bath into which the pin andV block are placed may also be varied. The load is applied by a ratchetarrangement. Wear measurements made above the transition pressure, thatis, the load at which the lubricant film breaks down, can be a usefulparameter if carried out under conditions comparable to actualoperations.

The following example is offered for illustration purposes and not byway of limitation.

EXAMPLE 1

This example illustrates 4-Ball and Falex Wear Test results for a 100SUS solvent paraffinic mineral oil base fluid without a lubricantadditive and with different lubricant additives as indicated. Thisexample compares the model test system properties of lubricant additivescomposed of one component as compared with lubricant additives composedof two or three components.

                  TABLE 3                                                         ______________________________________                                                          4-Ball Wear                                                                              Falex                                                                Wear Scar Load   lbs to                                   Lubricant           Dia. (mm) (lbs)  Failure                                  ______________________________________                                        Base fluid          0.94      120     725                                     Base fluid + 1% meadowfoam oil                                                                    0.82      150    2600                                     Base fluid + 2% sulfurized                                                                        0.55      210    4200                                     meadowfoam oil.sup.a                                                          Base fluid + 1% meadowfoam                                                                        0.55      210    4200                                     phosphite adduct.sup.b                                                        Base fluid + 2% sulfurized                                                                        0.42      280    4500                                     meadowfoam oil.sup.a + 0.5% meadow-                                           foam phosphite adduct.sup.b                                                   Base fluid + 1% meadowfoam oil +                                                                  0.42      280    4500                                     1% sulfurized meadowfoam oil.sup.a +                                          0.5% meadowfoam phosphite adduct.sup.b                                        Base fluid + 1% meadowfoam oil                                                                    0.50      250    4000                                     + 0.5% meadowfoam phosphite                                                   adduct                                                                        ______________________________________                                         .sup.a The sulfurized meadowform oil is a mixture of 10 grams of              triglyceride meadowfoam oil and 10 grams of jojoba oil sulfurized with 4      grams of sulfur (Run #5 in Table 1).                                          .sup.b The meadowfoam phosphite adduct is a monoadduct of dibutyl             phosphite with triglyceride meadowfoam oil.                              

The principles, preferred embodiments, and modes of operation of theinvention have been described in the foregoing specification. Theinvention which is intended to be protected herein, however, is not tobe constrained as limited to the particular forms disclosed, since theseare to be regarded as illustrative rather than restrictive. Variationsand changes may be made by those skilled in this art without departingfrom the spirit and scope of the invention.

We claim:
 1. A lubricating composition consisting essentially of alubricant base and a lubricant additive wherein the lubricant additivecomprises a mixture of at least two ingredients from different classesof ingredients wherein the classes of ingredients are selected from thegroup consisting of:a first class of ingredients selected from the groupconsisting of a triglyceride vegetable oil, a wax ester of atriglyceride vegetable oil, and combinations thereof; a second class ofingredients comprising a sulfurized mixture of from about 25% to about75% of the triglyceride vegetable oil and from about 25% to about 75% ofthe wax ester of triglyceride vegetable oil, wherein said wax ester isderived from a C₁₈₋₂₂ unsaturated acid and a C₁₈₋₂₂ unsaturated alcoholor from about 25% to about 75% of jojoba oil; and a third class ofingredients is selected from the group consisting of a phosphite adductof triglyceride vegetable oil, a phosphite adduct of the wax ester, andcombinations thereof, with the proviso that at least 90% of the fattyacids of the vegetable oil are from about 16 to about 26 carbon atomslong and have at least one and no more than three double bonds.
 2. Thelubricating composition of claim 1 wherein the vegetable oil is selectedfrom the group consisting of rapeseed oil, crambe oil and combinationsthereof.
 3. The lubricating composition of claim 1 wherein thelubricating composition comprises from about 0.1% to about 25% of thelubricant additive.
 4. The lubricating composition of claim 1 whereinthe third class of ingredients is a mono-, di-, tri-, tetra-, penta- orhexa-adduct of the reaction product ofand triglyceride vegetable oil,wherein R is selected from the group consisting of H, C₁₋₁₂ alkyl, C₁₋₁₂aryl, C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₄₋₁₂ alkyl.
 5. Thelubricating composition of claim 4 wherein R is selected from the groupconsisting of C₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, and cyclo C₄₋₈alkyl.
 6. The lubricating composition of claim 5 wherein R is n-butyl.7. The lubricating composition of claim 1 wherein the lubricant additivecomprises from about 0.1% to about 20% of the triglyceride vegetableoil, from about 0.1% to about 10% of the sulfurized triglyceridevegetable oil, and from about 0.1% to about 5% of the phosphite adductof triglyceride vegetable oil.
 8. The lubricating composition of claim 1wherein the lubricant additive comprises from about 0.1% to about 5% ofthe triglyceride vegetable oil, from about 0.2% to about 10% of thesulfurized triglyceride vegetable oil, and from about 0.1% to about 5%of the phosphite adduct of triglyceride vegetable oil.
 9. Thelubricating composition of claim 1 wherein the lubricant additivecomprises from about 0.1% to about 20% of the triglyceride vegetableoil, and from about 0.1% to about 5% of the phosphite adduct of thetriglyceride vegetable oil.
 10. The lubricating composition of claim 1wherein the lubricant base is selected from the group of lubricant basesuseful for an automobile engine oil, a precoat oil, a gear lubricant, atextile lubricant, an aviation oil, a grease, a hydraulic oil, acirculating oil, a diesel engine oil, an automatic transmission fluid, away lubricant, a steam cylinder oil, a spindle oil, and a cutting fluid.11. A lubricant additive comprising a mixture of at least twoingredients from different classes of ingredients wherein the classes ofingredients are selected from the group consisting of:a first class ofingredients selected from the group consisting of a triglyceridevegetable oil, a wax ester of a triglyceride vegetable oil, andcombinations thereof; a second class of ingredients comprising asulfurized mixture of from about 25% to about 75% of the triglyceridevegetable oil and from about 25% to about 75% of the wax ester oftriglyceride vegetable oil, wherein said wax ester is derived from aC₁₈₋₂₂ unsaturated acid and a C₁₈₋₂₂ unsaturated alcohol or from about25% to about 75% of jojoba oil; and a third class of ingredients isselected from the group consisting of a phosphite adduct of triglyceridevegetable oil, a phosphite adduct of the wax ester, and combinationsthereof, with the proviso that at least 90% of the fatty acids of thevegetable oil are from about 16 to about 26 carbon atoms long and haveat least one and no more than three double bonds.
 12. The lubricantadditive of claim 11 wherein the vegetable oil is selected from thegroup consisting of rapeseed oil, crambe oil and combinations thereof.13. The lubricant additive of claim 11 wherein the third class ofingredients is a mono-, di-, tri, tetra-, penta- or hexa-adduct of thereaction product of ##STR9## and triglyceride vegetable oil, wherein Ris selected from the group consisting of H, C₁₋₁₂ alkyl, C₁₋₁₂ aryl,C₁₋₁₂ alkaryl, C₁₋₁₂ aralkyl, and cyclo C₄₋₁₂ alkyl.
 14. The lubricantadditive of claim 13 wherein R is selected from the group consisting ofC₄₋₈ alkyl, C₄₋₈ alkaryl, C₄₋₈ aralkyl, and cyclo C₄₋₈ alkyl.
 15. Thelubricant additive of claim 14 wherein R is n-butyl.
 16. The lubricantadditive of claim 11 wherein the phosphite adduct point of attachment totriglyceride vegetable oil, or the wax ester of the vegetable oil is ata carbon-carbon double bond.
 17. The lubricant additive of claim 11wherein the lubricant additive comprises from about 0.1% to about 20% ofthe triglyceride vegetable oil, from about 0.1% to about 10% of thesulfurized mixture and from about 0.1% to about 5% of the phosphiteadduct of triglyceride vegetable oil.
 18. The lubricant additive ofclaim 17 wherein the lubricant additive comprises from about 0.1% toabout 5% of the triglyceride vegetable oil, from about 0.2% to abut 10%of the sulfurized triglyceride vegetable oil and from about 0.1% toabout 5% of the phosphite adduct of triglyceride vegetable oil.
 19. Thelubricant additive of claim 11 wherein the lubricant additive comprisesfrom about 0.1% to about 20% of the triglyceride vegetable oil and fromabout 0.1% to about 5% of the phosphite adduct of triglyceride vegetableoil.